Ligand-Enhanced Optical Response of Gold Nanomolecules and Its Fragment Projection Analysis: The Case of Au 30 (SR) 18

Sementa, Luca; Barcaro, Giovanni; Baseggio, Oscar; De Vetta, Martina; Dass, Amala; Apr?, Edoardo; Stener, Mauro; Fortunelli, Alessandro

doi:10.1021/acs.jpcc.6b12029

Ligand-Enhanced Optical Response of Gold Nanomolecules and Its Fragment Projection Analysis: The Case of Au ₃₀ (SR) ₁₈

Journal Article · Tue Jan 10 04:00:00 EST 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b12029· OSTI ID:1364002

Sementa, Luca; Barcaro, Giovanni; Baseggio, Oscar; De Vetta, Martina; ; ; ;

Here we investigate via first-principles simulations the optical absorption spectra of three different Au30(SR)18 monolayer-protected clusters (MPC): Au30(StBu)18, which is known in the literature and whose crystal structure is available, and two species – Au30(SPh)18 and Au30(SPh-pNO2)18 – which have been designed by replacing the tert-butyl organic residues with aromatic ones so as to investigate the effects of ligand replacement on the optical response of Au nanomolecules. In analogy with previously studied but rather different Au23(SR)16- anionic species, a substantial ligand-enhancement of the absorption intensity in the optical region is obtained for the Au30(SPhpNO2)18 neutral MPC. This demonstrates that using conjugated aromatic ligands with properly chosen electron withdrawal substituents and exhibiting steric hindrance so as to also achieve charge decompression at the surface is a general approach to enhance MPC photo-absorption intensity in the optical region. Moreover, the ligand-enhancement phenomenon is subjected to a detailed analysis based on fragment projection of electronic excited states and on induced transition densities, leading to a better understanding of its physical origin, thus opening avenues to its more precise control and exploitation.

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1364002

Report Number(s):: PNNL-SA-123164; 49097; 49645; KP1704020

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 20 Vol. 121; ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

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